WO1996032368A1 - One-pot synthesis of ring-brominated benzoate compounds - Google Patents
One-pot synthesis of ring-brominated benzoate compounds Download PDFInfo
- Publication number
- WO1996032368A1 WO1996032368A1 PCT/US1996/005031 US9605031W WO9632368A1 WO 1996032368 A1 WO1996032368 A1 WO 1996032368A1 US 9605031 W US9605031 W US 9605031W WO 9632368 A1 WO9632368 A1 WO 9632368A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alcohol
- methyl
- dimethyl
- hexanol
- tetrabromobenzoate
- Prior art date
Links
- 0 *c(c(Br)c(cc1C(O*)=O)Br)c1Br Chemical compound *c(c(Br)c(cc1C(O*)=O)Br)c1Br 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
- C07C67/32—Decarboxylation
Definitions
- the present invention relates generally to methods for synthesizing tetrabromobenzoates, and more particularly to a method for their one-pot synthesis in high yield from tetrabromophthalic anhydride.
- tetrabromobenzoates have been disclosed by the prior art as being a minor, undesirable by-product in the synthesis of tetrabromophthalates from tetrabromophthalic anhydride.
- ⁇ e .g. r U.S. Patent Nos. 5,049,697 and 5,208,366, both to Bohen et al ; and Spatz et al . , 8 Ind. Eng. Chem. Prod. Res. Develop., 391 (1969) .
- tetrabromobenzoate is formed through decarboxylation of a reaction intermediate, and conditions are stated by which this undesirable side-reaction can be avoided.
- tetrabromobenzoate compounds from tetrabromophthalic anhydride.
- a one-pot method is disclosed wherein tetrabromobenzoates are prepared by reacting tetrabromophthalic anhydride with the appropriate alcohol in the presence of a decarboxylation catalyst. The reaction proceeds through rapid esterification of the anhydride, followed by decarboxylation to yield the tetrabromobenzoate.
- One object of the present invention is to provide a faster, less expensive method of synthesizing tetrabromobenzoates from tetrabromophthalic anhydride. Further objects and advantages of the invention will be apparent from the following description.
- the present invention relates to a method for converting tetrabromophthalic anhydride to a selected tetrabromobenzoate.
- tetrabromophthalic anhydride is reacted with the appropriate alcohol in the presence of a decarboxylation catalyst.
- the reaction is performed in an inert solvent to further minimize the creation of phthalates.
- R is an organic group provided by the alcohol used in the reaction, the organic group preferably having up to about 30 carbon atoms, and optionally being substituted with one or more groups such as alkoxy, halo, amino, thio, and the like.
- Alcohols useful in the present invention include alcohols having a boiling point of between about 160°C and about 230°C, preferably between 180°C and 205°C. These alcohols provide the advantage of allowing the decarboxylation reaction to proceed at a reasonable rate, while still allowing for ease of stripping the excess alcohol from the product at the end of the reaction.
- the alcohol is a non-halogenated, non-sulfur-containing, non-nitrogen-containing alcohol. Branched chain alcohols are most preferred.
- Appropriate alcohols with boiling points between about 160°C and about 230°C include 2- (2- methoxy) ethoxyethanol, 2-butoxyethanol, 3, 3-diethoxy-l- propanol, di (propylene glycol) methyl ether, 2-ethyl-1- hexanol, 3-ethyl-l-hexanol, 3 ,4-dimethyl-1-hexanol, 3,5- dimethyl-1-hexanol, 3-methyl-1-heptanol, 4-methyl-l- heptanol, 2-octanol, 5-methyl-1-heptanol, 3-octanol, 2- propyl-1-pentanol, 2, 6-dimethyl-4-heptanol, 2-nonanol, dihydromyrcenol, 3, 5, 5-trimethyl-1-hexanol, 3,7- dimethyl-1-octanol, 3 , 7-dimethyl-3-octanol
- alcohols with boiling points below 160°C can be used in combination with a high boiling solvent.
- alcohols with boiling points between about 100°C and 160°C may advantageously be used in that manner.
- Preferred are non-halogenated, non- sulfur-containing, non-nitrogen-containing alcohols with boiling points between about 130°C and 160°C. Branched chain alcohols are most preferred.
- Examples of appropriate alcohols with boiling points lower than about 160°C include 2-ethoxyethanol, amyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3- ethoxy-1-propanol, 2-ethyl-1-butanol, 4-methyl-2- pentanol, 2,4-dimethyl-3-pentanol, acetol, 2-butyne-l- ol, 3-butyn-l-ol, l-pentyn-3-ol, 2-pentyn-l-ol, 3- pentyn-1-ol, 4-pentyn-l-ol, 4-pentyn-2-ol, cyclobutanemethanol, 3-methyl-2-buten-l-ol, 3-methyl-3- buten-1-ol, 2-penten-l-ol, 4-penten-l-ol, 1-pentanol, cyclohexanol, l-hexen-3-ol, 2-hexen-
- the decarboxylation reaction can be carried out using any appropriate catalyst that favors decarboxylation over esterification, for example providing in the reaction at hand a reaction product at least 50% by weight comprised of the desired ring- brominated benzoate compound.
- Preferred catalysts include alkali carbonates, alkali bicarbonates and caustic alkalis. Sodium and potassium carbonate and bicarbonate, lithium carbonate and sodium aluminate are particularly preferred due to their relatively low cost and ready availability.
- the catalyst loading effects the product ratio of tetrabromobenzoate to tetrabromophthalate ester. With a lower catalyst loading, the decarboxylation step is slower, which allows greater formation of diester. With a higher catalyst loading, lower amounts of diester are formed but increasing amounts of other by-products have been observed.
- the desired catalyst loading is between 1 and 25 mole percent, and preferable between 5 and 15%, based upon the tetrabromophthalic anhydride charge. Some catalysts yield a lighter colored product.
- the reaction may be accomplished in an excess of alcohol (e.g.. 3 to 6 mole equivalents based on the tetrabromophthalic anhydride used) , although an inert solvent may alternatively be used.
- alcohol e.g. 3 to 6 mole equivalents based on the tetrabromophthalic anhydride used
- an inert solvent may alternatively be used.
- the reaction is carried out in an inert solvent, such as a high boiling ether, with near stoichiometric amounts of the alcohol (e.g.. 1.0 to 1.25 mole equivalents).
- inert solvents particularly preferred for the invention have a boiling point of between about 160°C and about 230°C, and are preferably from the family of ethers such as, for example, 2-ethoxyethylether.
- the inert solvent should have solubility properties which allow the reaction to proceed at a reasonable rate, particularly by accommodating the solubility of the polar intermediate (or its salt complex) .
- a low viscosity liquid product which contains 50-90% tetrabromobenzoate and 1-40% of the corresponding phthalate.
- the one-pot process provides at least about 60% tetrabromobenzoate, while other preferred aspects provide at least about 70% tetrabromobenzoate. Further preferred embodiments provide at least about 80% tetrabromobenzoate, with one aspect of the invention providing at least about 85% tetrabromobenzoate.
- the total organic bromine content of the product which is an important factor for efficiency as a flame retardant, can be adjusted by the alcohol and/or solvent used in the synthesis and/or the catalyst loading, but generally falls within the range of 50-70%.
- a near stoichiometric amount of alcohol is reacted with tetrabromophthalic anhydride in an inert solvent to produce product comprising at least about 85% tetrabromobenzoate compound.
- the ring-brominated benzoates produced in accordance with the invention are useful as flame retardants in a variety of polymer resin systems.
- the bromobenzoate compound can be incorporated into thermoset polymers such as polyurethanes by including the bromobenzoate in the polyurethane mixture as the polymer is prepared. This process has been referred to as the "one-shot” technique, and is described with more particularity in common reference materials such as the Modern Plastics Encyclopedia, Vol. 71, No. 12 (1994), and was used in Examples 11 through 15 below.
- bromobenzoates into polyvinyl chlorides may be accomplished either by including the desired tetrabromobenzoate in the mixture as the polyvinyl chloride is being formed, or by incorporating the bromobenzoate into polymerized polyvinyl chloride.
- Specific techniques for incorporating additives such as bromobenzoates into thermoplastics such as PVC are known to the art and may be used to accomplish that step.
- the level of bromobenzoate incorporated into the polymer resin to provide an effective flame retarding amount will vary widely in accordance with many factors such as the particular resin used, the application contemplated, other additives present, etc.
- the bromobenzoate will be incorporated at levels between about 2% and 50% of the total system weight, and more commonly at levels between about 5% and 30% of the total system weight.
- the bromobenzoate product can be incorporated along with other brominated flame retardant compounds; however, it is preferred in this regard that the bromobenzoate compound constitute a predominant portion (i.e. greater than 50% by weight) of the total amount of brominated flame retardant included in the system.
- Flame retardant materials such as oxides of Group V elements, especially antimony oxides, and/or phosphorous-containing compounds, can also be included.
- Additional conventional additives may include antioxidants, antistatic agents, colorants, fibrous reinforcements, fillers, foaming/blowing agents, catalysts, heat stabilizers, impact modifiers, lubricants, plasticizers, processing aids, UV light stabilizers, crosslinking/curing agents, etc.
- Tetrabromophthalic anhydride (232g, 0.50 moles)
- 2- ethylhexanol (196g, 1.5 moles)
- sodium bicarbonate 232g, 0.50 moles
- Tetrabromophthalic anhydride (232g, 0.50 moles) , 2- ethylhexanol (196g, 1.5 moles) , and potassium bicarbonate (5.5g, 0.055 moles) were charged to a stirred, glass vessel. The mixture was heated to reflux, with the water of reaction being collected in a Dean-Stark trap. After CO2 evolution ceased (approx.
- Tetrabromophthalic anhydride (464g, 1.0 moles)
- 2- ethylhexanol (391g, 3.0 moles)
- potassium carbonate
- Tetrabromophthalic anhydride (464g, 1.0 moles) , 2- ethylhexanol (390g, 3.0 moles) , and lithium carbonate (8.1g, 0.11 moles) were charged to a stirred, glass vessel. The mixture was heated to reflux, with the water of reaction being collected in a Dean-Stark trap. After CO2 evolution ceased (approximately 8.0 hours) , the reaction was cooled and filtered to remove the catalyst. The excess 2-ethylhexanol was stripped off under vacuum yielding a clear, amber liquid product. GLC assay 60.7% tetrabromobenzoate, 10.4% tetrabromophthalic diester; OBr 51.9%; TGA 5% wt . loss 240°C.
- Tetrabromophthalic anhydride (232g, 0.5 moles), 2- butoxyethanol (226g, 1.9 moles), and potassium bicarbonate (8.3g, 0.083 moles) were charged to a stirred, glass vessel. The mixture was heated to reflux, with the water of reaction being collected in a Dean-Stark trap. After CO2 evolution had ceased (approximately 3 hours) , the reaction was cooled and filtered to remove the catalyst. Excess 2-butoxyethanol was stripped off under vacuum yielding a clear, amber product. GLC assay 82.4% tetrabromobenzoate, 7.9% tetrabromophthalic diester; OBr 57.84%; TGA 5% wt. loss 225°C; Gardner color 13.
- Tetrabromophthalic anhydride (232g, 0.5 moles), 2- methoxyethoxyethanol (238g, 2.0 moles), and potassium bicarbonate (8.3g, 0.083 moles) were charged to a stirred, glass vessel. The mixture was heated to reflux, with the water of reaction being collected in a Dean-Stark trap. After CO 2 evolution had ceased
- the 2-ethylhexyltetrabromobenzoate prepared in Example 1 was added to flexible polyurethane foam prepared by the formulation below. All components are expressed in parts by weight.
- RIM system contains 15% of a blend of pentabromodiphenyl oxide and an aromatic phosphate ester (DE-60FS) as a combustibility modifier. RIM parts were molded containing this standard combustion modifier and containing the same level (15%) of a 2:1 blend of 2- ethylhexyltetrabromobenzoate and triethyl phosphate
- the 2-ethylhexyltetrabromobenzoate of Example 1 was added to a rigid polyurethane foam as indicated in the formulation below.
- the resultant foam which had good cell structure and a density of 2.1 lbs. per cubic foot, was tested for combustibility in a four foot tunnel designed to correlate with the results obtained on a larger scale in the 25 foot tunnel test (ASTM E-84) .
- the four foot tunnel test consists of a Fisher burner with a 1950°F butane flame placed under a 4 foot long specimen inclined at an angle of fifteen degrees. Smoke is measured by passing combustion products between a light beam and photocell. Standards with known 25 foot tunnel test values are used for calibration.
- Polymeric MDI (N125 index) 80.6 Combustibility results of four foot tunnel testing of this foam were a predicted flame spread of 19 and smoke evolution of 170. Both are well within the requirements for Class 1 of less than 25 flame spread and 450 smoke for the 25 foot tunnel. Although tetrabromophthalate diol contributes to the combustibility test performance, over 60 parts of this diol are needed in this formulation when the tetrabromobenzoate is not present to attain less than 25 flame spread in the four foot tunnel test.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
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Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96909913A EP0825974A4 (en) | 1995-04-11 | 1996-04-09 | One-pot synthesis of ring-brominated benzoate compounds |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/420,125 | 1995-04-11 | ||
US08/420,125 US5637757A (en) | 1995-04-11 | 1995-04-11 | One-pot synthesis of ring-brominated benzoate compounds |
Publications (1)
Publication Number | Publication Date |
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WO1996032368A1 true WO1996032368A1 (en) | 1996-10-17 |
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ID=23665184
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Application Number | Title | Priority Date | Filing Date |
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PCT/US1996/005031 WO1996032368A1 (en) | 1995-04-11 | 1996-04-09 | One-pot synthesis of ring-brominated benzoate compounds |
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US (1) | US5637757A (en) |
EP (1) | EP0825974A4 (en) |
CA (1) | CA2217760A1 (en) |
IL (1) | IL117488A (en) |
WO (1) | WO1996032368A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111286083A (en) * | 2020-03-30 | 2020-06-16 | 广州埃登达化工有限公司 | Bromine flame retardant and preparation method thereof |
CN111499513A (en) * | 2020-04-24 | 2020-08-07 | 上海毕得医药科技有限公司 | Synthetic method of 2,3,4, 5-tetrabromobenzoate |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7008973B2 (en) * | 2003-01-14 | 2006-03-07 | Pabu Services, Inc. | Vacuum cooled foams |
US7307183B2 (en) * | 2003-07-29 | 2007-12-11 | Great Lakes Chemical Corporation | Process for producing tetrabromobenzoate esters |
JP4464921B2 (en) * | 2003-07-29 | 2010-05-19 | グレイト レイクス ケミカル コーポレイション | Method for producing tetrabromobenzoate ester |
PL1861458T3 (en) * | 2005-03-21 | 2010-09-30 | Chemtura Corp | Flame retardants and flame retarded polymers |
US20100113631A1 (en) * | 2006-11-17 | 2010-05-06 | Desikan Anantha N | Halobenzoate esters, flame retardant composition containing same and, polyurethane foam made therewith |
CN109776318B (en) * | 2019-03-27 | 2021-09-17 | 山东润科化工股份有限公司 | Synthesis method of tetrabromobenzoic acid-2-ethylhexyl ester |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5049697A (en) * | 1987-09-21 | 1991-09-17 | Atochem North America, Inc. | High yield method for preparation of dialkyl esters of polyhaloaromatic acids |
Family Cites Families (3)
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JPS5344602B2 (en) * | 1973-05-21 | 1978-11-30 | ||
JP2566976B2 (en) * | 1987-04-08 | 1996-12-25 | 日本カーバイド工業株式会社 | Method for decarboxylation of halogen-substituted benzenecarboxylic acid |
US5329054A (en) * | 1993-07-19 | 1994-07-12 | Albemarle Corporation | Decarboxylation process |
-
1995
- 1995-04-11 US US08/420,125 patent/US5637757A/en not_active Expired - Lifetime
-
1996
- 1996-03-14 IL IL11748896A patent/IL117488A/en not_active IP Right Cessation
- 1996-04-09 EP EP96909913A patent/EP0825974A4/en not_active Withdrawn
- 1996-04-09 WO PCT/US1996/005031 patent/WO1996032368A1/en not_active Application Discontinuation
- 1996-04-09 CA CA002217760A patent/CA2217760A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5049697A (en) * | 1987-09-21 | 1991-09-17 | Atochem North America, Inc. | High yield method for preparation of dialkyl esters of polyhaloaromatic acids |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111286083A (en) * | 2020-03-30 | 2020-06-16 | 广州埃登达化工有限公司 | Bromine flame retardant and preparation method thereof |
CN111499513A (en) * | 2020-04-24 | 2020-08-07 | 上海毕得医药科技有限公司 | Synthetic method of 2,3,4, 5-tetrabromobenzoate |
CN111499513B (en) * | 2020-04-24 | 2023-03-14 | 上海毕得医药科技股份有限公司 | Synthesis method of 2,3,4, 5-tetrabromobenzoate |
Also Published As
Publication number | Publication date |
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EP0825974A4 (en) | 1998-07-08 |
IL117488A (en) | 1999-10-28 |
CA2217760A1 (en) | 1996-10-17 |
US5637757A (en) | 1997-06-10 |
EP0825974A1 (en) | 1998-03-04 |
IL117488A0 (en) | 1996-07-23 |
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